Ceskoslovenska Akademie Ved

Czechoslovenska Akademie Ved

Otakar Mikes

Jiri Coupek

Petr Strop

Miroslava Krivakova

Jiri Hradil

The invention relates to preparation of synthetic macroporous ion-exchanaging materials by a ternary copolymerization of hydrophilic monomers containing non-ionogenous groups with monomers containing ionogenous groups and cross-linking monomers in an aqueous dispersion in the presence of inert components and suspension stabilizers. Hydroxyalkyl, oligoglycol and polyglycol esters and N-substituted or unsubstituted amides of acrylic and methacrylic acid are used as the hydrophilic monomers; compounds CH.sub.2 .dbd.C(R)COX, where R = H or CH.sub.3, X = --OR.sub.1 N(R.sub.2)R.sub.3, --OR.sub.1 SO.sub.3 H, --NHR.sub.1 N(R.sub.2)R.sub.3 or --HNR.sub.1 SO.sub.3 H, R.sub.1 = alkylene and R.sub.2 and R.sub.3 = H, alkyl, hydroxyalkyl or aminoalkyl, acrylic and methacrylic acid serve as the ionogenous monomers; the crosslinking agents are selected from a group of monomers consisting of alkylene, oligoglycol or polyglycol diacrylates and dimethacrylates, alkylenebisacrylamides, alkylenebismethacrylamides, divinylbenzene and other compounds containing more than 2 polymerizable acryloyl or methacryloyl groups. The invented materials are suitable above all for isolation and chromatographic separation of sensitive compounds of the biological origin.

Method for preparation of hydrophilic polymeric ion exchanging gels

The invention relates to a method for preparation of ion exchangers from hydrophilic anion-exchanging gels based on acrylate or methacrylate copolymers prepared by copolymerization of amino-group-containing monomers, as aminoalkyl acrylates and methacrylates, aminoalkylacrylamides and aminoalkylmethacrylamides or on gels prepared by chemical bonding of amine groups to the hydrophilic matrix of acrylate or methacrylate copolymers. The method consists in alkylation or hydroxyalkylation of amine groups by alkylating agents, as alkyl halogenides, alkyl p-toluenesulfonates, alkyl sulfates, epoxides, etc. Alkylation with alkyldiaze compounds was used for transformation of the undesired carboxylic groups of the ion exchangers. Another modification consists in the reaction of halogenated acrylate or methacrylate gels with polyamines or oligomeric polyethyleneimines. These reactions lead to ion exchangers with modified chemical nature, dissociation constant, exchange capacity, degree of hydrophility, distance of the ionogenous groups from the surface of the matrix or the character of microsurroundings. The resulting ion-exchanging materials are suitable above all for the sorption and separation of biopolymers.

Method of preparation of ion exchangers by alkylation and

The invention relates to a method for preparation of hydrophilic anion exchangers from gels based on crosslinked copolymers of hydroxyalkyl acrylates and methacrylates, oligo- and polyglycol monoacrylates and monomethacrylates, hydroxyalkylacrylamides or hydroxyalkylmethacrylamides with crosslinking comonomers containing 2 or more acrylcyl or methacryloyl groups in the molecule, as alkylene, oligo- and polyglycol diacrylates and dimethacrylates or divinylbenzene, which gels may have the homogeneous, heterogeneous or macroporous character. The hydroxyl groups of the initial hydrophilic gel are modified by the reaction with halogenoalkylamines, halogenoalkylammonium compounds, epoxyalkylamines and epoxyalkylammonium compounds or with compounds having several reactive groups in the molecule, as epichlorohydrine, di- and polyepoxides, di- and polyisocyanates, halogenoalkylepoxides, epoxyalkylamines and phosgene, and the subsequent reaction with compounds rendering anion-exchanging groups, as hydroxyalkylamines, diamines and their ammonium compounds. The later procedure may be carried out in one step. The hydroxyl groups of the initial gel can be also substituted by halogens and transformed into quaternary ammonium compounds by reaction with amines. All reactions may be performed also with gels combining alkoxide instead of hydroxyl groups.

Method for preparation of anion exchangers by substitution of

The invention relates to a method for preparation of hydrophilic macroporous ion exchangers of the amphoteric character which are suitable above all for isolation and separation of biological materials. The preparation consists in copolymerization of anionogenous monomers, as sulfoalkyl acrylates and methacrylates, sulfoalkylacrylamides, sulfoalkylmethacrylamides, acrylic and methacrylic acid, with cationogenous monomers, as aminoalkyl acrylates and methacrylates, aminoalkylacrylamides, aminoalkylmethacrylamides and their quaternary ammonium derivatives, and with crosslinking monomers, as alkylene or oligo and polyglycol diacrylates and dimethacrylates, bisacrylamides, bismethacrylamides and divlnylbenzene, in the water dispersion system containing inert organic compounds, as alcohols, acids, amines or nitriles. Amphoteric ion exchangers are also prepared by sorption and neutralization of the macroporous hydrophilic cation exchangers with basic monomers, as vinylpyridines, aminoalkyl acrylates and methacrylates, aminoalkylacrylamides, aminoalkylmethacrylamides and their quaternary ammonium derivatives, and their subsequent copolymerization with the pendant double bonds of the cation exchangers. An analogous procedure was performed with macroporous hydrophilic anion exchangers and the acidic monomers, as sulfoalkyl acrylates and methacrylates, sulfoalkylacrylamides, sulfoalkylmethacrylamides, acrylic and methacrylic acid. Another methods for preparation of amphoteric ion exchangers consists in modification of hydroxyl groups of crosslinked acrylate, methacrylate, acrylamide and methacrylamide copolymers by parallel reactions with anionogenous and cationogenous compounds, as halogenoalkylamines, their ammonium compounds and halogenoalkane acids or in the reaction of these copolymers first with a compound containing several reactive groups in its molecule, as phosgene, epichlorohydrine, di- and polyepoxide, di- and polyisocyanate, and then with compounds rendering anions and cations or dipolar ions by dissociation, as diamines, aminoacids, hydroxyacids, and dicarboxylic acids. For this purpose, the activation of hydroxyl groups with cyanogen bromide can be used in the first step. Hydrophilic amphoteric ion exchangers may be also prepared by quaternization of amino groups in crosslinked copolymers by means of halogenoalkane acids.

Method for preparation of macroporous amphoteric ion exchangers with

The invention relates to a method for preparation of hydrophilic cation exchangers by a chemical modification of crosslinked copolymeric gels containing reactive hydroxyl groups and based on hydroxyalkyl, oligoglycol or polyglycol acrylates and methacrylates and hydroxyalkylacrylamides or hydroxyalkylmethacrylamides. The modification is carried out in reactions of hydroxyl groups with halogenalkane acids and their derivatives, anhydrides and halides of dicarboxylic acids or carbodiimides. If the modification agent contains several reactive groups, the remaining functional groups after modification may be allowed to react with dicarboxylic, polycarboxylic, hydroxycarboxylic or aminocarboxylic acids, or phosphoric or sulfuric acid, halogenoepoxides, diepoxides or polyepoxides. The hydroxyl groups can be also modified by oxidation to carboxylic groups by common oxidants. The gels used for modification may also contain alkoxide reactive groups and they have generally the homogeneous, semiheterogeneous or macroporous character. The ion-exchanging gels prepared in this way are suitable for sorption and chromatographic separations, especially for separation of sensitive biological materials.

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Otakar Mikes